WO2009082260A1 - Installation destinée à la synthèse d'isoprène en phase liquide à partir d'isobutylène et de formaldéhyde - Google Patents
Installation destinée à la synthèse d'isoprène en phase liquide à partir d'isobutylène et de formaldéhyde Download PDFInfo
- Publication number
- WO2009082260A1 WO2009082260A1 PCT/RU2008/000367 RU2008000367W WO2009082260A1 WO 2009082260 A1 WO2009082260 A1 WO 2009082260A1 RU 2008000367 W RU2008000367 W RU 2008000367W WO 2009082260 A1 WO2009082260 A1 WO 2009082260A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- synthesis
- unit
- products
- isoprene
- decomposition
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
Definitions
- This utility model relates to devices used in the production of monomers for synthetic rubber, in particular, to the arrangement and interconnection of apparatus for the synthesis of isoprene in the liquid phase from isobutylene and formaldehyde or substances that are sources of isobutylene and formaldehyde, for example, trimethylcarbinol (TMK) or dimethyldioxane (DMD), in the presence of an aqueous solution of an acid catalyst.
- TMK trimethylcarbinol
- DMD dimethyldioxane
- the known design of the reactor block which includes two series-connected apparatus - an airlift column and a shell-and-tube column with an external circulation loop connecting the upper separation and lower reaction zones, with distribution devices located in the lower part of the columns and equipped with ring rings installed on the inner surface of the reactor pipes at the same height restrictions intended to increase the actual residence time of the reactants in the reaction volume (RF patent 2096076, publ. 199 four).
- a similar switchgear is installed at the bottom the heat exchanger (under the tube sheet) on the same axis as the pipe axis connecting this apparatus to the reactor (above the upper tube sheet). From the lowest point of the spherical part of the reactor, a second pipe leaves, connecting the reactor with the lower zone of the heat exchanger located below the tube sheet, and from the highest point of the reactor leaves a pipe designed to divert contact gas to the separator (RF patent Nb 32706, publ. 2003, )
- This design provides good mixing of the reaction mass and, no less important, the effective removal of isoprene in the isobutylene stream from the reaction zone, however, its principal drawback is the presence of an external heat exchanger in its composition, which leads to an increase in the metal consumption of the installation (the cost of manufacturing heavy flanges and the body shell-and-tube heat exchanger), and most importantly - is associated with the inevitable heat loss.
- a simplified design of a liquid-phase synthesis plant for isoprene from isobutylene and formaldehyde is known, which allows for synthesis in one reaction zone (in one step), consisting of a vertically mounted hollow reactor, in which a shell-and-tube heat exchanger is designed to supply the heat necessary for the reaction and one or two circulation pipes connecting the upper and lower parts of the reactor, the diameter of which is not less than five times the diameter of the tubes of the heat exchanger.
- the hollow reactor vessel is at the same time a heat exchanger shell.
- the ratio of the volumes of the upper and lower parts of the hollow reactor, separated by an integrated heat exchanger, is at least 2-2.5.
- the reaction mass is circulated in the tubes of the heat exchanger due to the difference in the densities of gas and liquid. For intensification of mixing can be used forced circulation using a pump.
- Both parts of the reactor contain switchgears designed for supplying raw materials.
- Switchgears are a system of tubes with holes with a diameter of 2-5 mm parallel to the central (feed) pipe.
- the area of the distribution devices, calculated according to their overall dimensions, is not more than 25% of the cross section of the vessels in which they are installed (RF Patent N °
- the installation includes 2-4 series-connected reactors for the interaction of an acidic aqueous solution of formaldehyde with isobutylene and / or trimethylcarbinol at a temperature of 150-220 0 C and a pressure 1-2-5 times higher than the vapor pressure of the reaction mixture at these temperatures.
- Isobutylene and / or trimethylcarbinol is fed only to the first reactor, and formalin to each reactor.
- Isoprene, water, unconverted starting products are distilled off from each reaction zone and introduced into the next one with distillation from the last reaction zone.
- the yield of isoprene on converted formaldehyde and isobutylene is insufficient and is 52 and 74%, respectively.
- the installation consists of several connected reactors (blocks) for the synthesis of isoprene precursors and a decomposition unit for the resulting products. Between the synthesis units and the decomposition unit, one or two distillation columns are installed. The installation includes a unit for separation of products formed in the decomposition reactor.
- the disadvantage of the described installation is the formation of a large number of high boiling point by-products and their accumulation in the system, which leads to the formation of non-stratifying emulsions and solid deposits on the equipment and its clogging, especially when the installation is operated in an industrial environment.
- This is due to the ingestion of high boiling point by-products (BCHI) in the specifics of their heavy part are formal dioxane alcohols formed during the synthesis of isoprene precursors, in particular DMD, into a decomposition unit that operates at high operating temperatures (130-170 0 C) and a high concentration of acid catalyst.
- BCHI high boiling point by-products
- runways which are a mixture of dioxane alcohols and their derivatives, turn into the so-called “green oil”, which can only be used as low-calorie fuel, while runways are widely used in the national economy and their price is much higher than the cost raw materials.
- the installation according to the closest analogue does not provide for heterogeneous catalytic decomposition of the pyran fraction, which also affects the technical and economic performance of the process.
- TMK in block 1 serves IIF and water.
- the synthesis of TMK is carried out in shelf reactors filled with cation exchanger.
- the returning fraction IIF from block 1 is sent to the warehouse.
- the resulting TMK after separation from the return IIP is fed to isoprene synthesis unit 4, where DMD is simultaneously supplied from block 3.
- the required amount of DMD is synthesized in block 3, for which IIF, formaldehyde and the water layer from block 4 are fed there.
- the return fraction of IIF from block 3 is sent to the warehouse.
- the isoprene-containing fraction formed in block 4 is fed to the separation of synthesis products and the separation of the isoprene monomer into block 7, and concentrated isobutylene distilled in block 4 and block 7 is returned to TMK synthesis block 2 from concentrated isobutylene. At the same time, water is supplied to the synthesis unit 2.
- High-boiling by-products formed in the synthesis of DMD from block 3 are fed to the rectification unit 5 of high-boiling by-products of the synthesis of DMD, in which there is a separation into light by-products and heavy by-products, which are then sent for sale. All or part of the light high boiling point by-products may be sent to the by-product decomposition unit 6.
- By-products (4-methyl-5,6-dihydro- ⁇ -pyran (MDHP) fraction) from block 7, which are formed during the synthesis of isoprene, are simultaneously fed to block 6.
- the isoprene-containing fraction from block 6 is fed to the separation of synthesis products and the separation of isoprene monomer in block 7, in which the isolation of commercial isoprene rectified and separation of by-products occurs.
- the utility model contains technical solutions to reduce the specific metal consumption of the process, increase productivity, ensure uninterrupted operation of industrial equipment of the technological unit for one year, and also use the resulting by-products in a qualified manner.
- TMK-based process without using pure isobutylene in block 4 allows the process to be carried out at lower reagent ratios (isobutylene source / formaldehyde source), due to the fact that TMK dehydration proceeds in the volume of the aqueous phase in which formaldehyde and acid catalyst are located, due to which the likelihood of a “conversion” of isobutylene with formaldehyde increases sharply and, accordingly, the rate of their interaction increases.
- the industrial use of the proposed installation achieved the following indicators:
- block 6 decomposition of by-products (in particular 1 ton of technical pyranic fraction) allows you to get an additional -490 kg of isoprene and -220 kg of formaldehyde, which significantly (-5%) reduces the consumption ratios for raw materials.
- the implementation of the heavy runway fraction at the rate of -140 kg per lt of isoprene obtained in block 5 allows to reduce the cost of the target product by 5%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008801272383A CN101970387A (zh) | 2007-12-21 | 2008-06-09 | 源自异丁烯和甲醛的异戊二烯液相合成装置 |
EP08794018A EP2236484A4 (de) | 2007-12-21 | 2008-06-09 | Anlage für die flüssigphasensynthese von isopren aus isobutylen und formaldehyd |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2007147962 | 2007-12-21 | ||
RU2007147962 | 2007-12-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009082260A1 true WO2009082260A1 (fr) | 2009-07-02 |
Family
ID=40801396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/RU2008/000367 WO2009082260A1 (fr) | 2007-12-21 | 2008-06-09 | Installation destinée à la synthèse d'isoprène en phase liquide à partir d'isobutylène et de formaldéhyde |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2236484A4 (de) |
CN (1) | CN101970387A (de) |
WO (1) | WO2009082260A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2459790C1 (ru) * | 2011-07-27 | 2012-08-27 | Закрытое Акционерное Общество "Сибур Холдинг" | Способ получения изопрена |
CN103814004A (zh) * | 2011-08-17 | 2014-05-21 | 史波柏·优乐庆有限公司 | 从异丁烯和甲醛合成异戊二烯的液相合成装置 |
CN103467234A (zh) * | 2013-09-04 | 2013-12-25 | 山东垦利石化集团有限公司 | 烯醛合成异戊二烯工艺技术 |
CN106278790B (zh) * | 2015-06-05 | 2018-09-11 | 中国科学院大连化学物理研究所 | 一种制备异戊二烯的方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4511751A (en) | 1982-10-14 | 1985-04-16 | Kuraray Company, Ltd. | Process for producing isoprene |
US4593145A (en) | 1984-03-12 | 1986-06-03 | Kuraray Company Limited | Process for producing isoprene |
RU2096076C1 (ru) | 1994-10-12 | 1997-11-20 | Акционерное общество Научно-производственное предприятие "Ярсинтез" | Аппарат для жидкофазного синтеза изопрена |
RU32706U1 (ru) | 2003-01-20 | 2003-09-27 | Общество с ограниченной ответственностью "Еврохим-СПб-Трейдинг" | Установка для жидкофазного одностадийного синтеза изопрена (варианты) |
RU42185U1 (ru) | 2004-07-27 | 2004-11-27 | Общество с ограниченной ответственностью "Еврохим-СПб-Трейдинг" | Установка для одностадийного жидкофазного синтеза изопрена |
RU2280022C1 (ru) | 2005-04-06 | 2006-07-20 | Олег Станиславович Павлов | Способ получения изопрена из изобутена и формальдегида |
RU2304135C1 (ru) * | 2006-05-31 | 2007-08-10 | Олег Станиславович Павлов | Способ получения изопрена |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3972955A (en) * | 1973-09-22 | 1976-08-03 | Bayer Aktiengesellschaft | Process for preparation of isoprene |
SU772074A1 (ru) * | 1979-01-24 | 1995-05-27 | В.Н. Чуркин | Способ выделения изопрена |
-
2008
- 2008-06-09 CN CN2008801272383A patent/CN101970387A/zh active Pending
- 2008-06-09 WO PCT/RU2008/000367 patent/WO2009082260A1/ru active Application Filing
- 2008-06-09 EP EP08794018A patent/EP2236484A4/de not_active Withdrawn
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4511751A (en) | 1982-10-14 | 1985-04-16 | Kuraray Company, Ltd. | Process for producing isoprene |
US4593145A (en) | 1984-03-12 | 1986-06-03 | Kuraray Company Limited | Process for producing isoprene |
RU2096076C1 (ru) | 1994-10-12 | 1997-11-20 | Акционерное общество Научно-производственное предприятие "Ярсинтез" | Аппарат для жидкофазного синтеза изопрена |
RU32706U1 (ru) | 2003-01-20 | 2003-09-27 | Общество с ограниченной ответственностью "Еврохим-СПб-Трейдинг" | Установка для жидкофазного одностадийного синтеза изопрена (варианты) |
RU42185U1 (ru) | 2004-07-27 | 2004-11-27 | Общество с ограниченной ответственностью "Еврохим-СПб-Трейдинг" | Установка для одностадийного жидкофазного синтеза изопрена |
RU2280022C1 (ru) | 2005-04-06 | 2006-07-20 | Олег Станиславович Павлов | Способ получения изопрена из изобутена и формальдегида |
RU2304135C1 (ru) * | 2006-05-31 | 2007-08-10 | Олег Станиславович Павлов | Способ получения изопрена |
Non-Patent Citations (1)
Title |
---|
See also references of EP2236484A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP2236484A4 (de) | 2012-01-18 |
EP2236484A1 (de) | 2010-10-06 |
CN101970387A (zh) | 2011-02-09 |
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